Production of valuable hydrocarbons



July 5,1938. K. wlNKLER 2,122,903

PRODUCTION OF VALUABLE HYDROCARBONS Filed sept.' 2.5, v193s or/er @www3/fs k l l Patzinted July v5, 1938 i y UNITED 'STATES PATENT; oFFicE wei? PaonUc'noN or vALUABLa ayunocannoNs 1 can.A (ol. iss-sz) The present invention relates to improvements;F

inthe production of valuable lhydrocarbons in. particular by cracking hydrocarbon oils.

Itis already known that certain metal halides. 5 especially aluminium chloride, iron chloride, tin lchloride and zinc chloridefexert a very favorable "action inthe thermal treatment of hydrocarbons. such as mineral oils and tars, both as regards splitting and as regards refining. It has already been proposed to use the corresponding metals and halogens instead of lthe already prepared metal halides. In most oft/he processes hitherto known, however, it is necessary to add Jarge amounts oithe said additional substances to the i8 oils or the liketobe treatedin order to obtain' a .satisfactory effect. Apart from the consequenthighpcost of the additions, there is alsov a very high waste of initial'materlals because the reaction takes place with the`simultanous forma- '20 tion of considerable'amounts of-.polymerlaation products.. Furthermore the large amounts of: halogenfhydracidsset free during the reaction lead to strongcorrosion of the apparatus which can only` .be overcome with aimcmty and wil-.1i

, considerable expense. Usually amounts for V ex-V ample of from 8`to loper cent of aluminium chloride (calculated with reference to lthe initial materlal) must'be employed in order to obtain a `yield of about 50 per cent oi' hydrocarbons of low boiling point. v Furthermoreit is usually only possible to work in discontinuous operation `and the =throughputs "per unit of time are very smallv ."'so thatflarge reaction vessels mustbe employed;

this is attended `by great diiliculty. The regenv veration' of the aluminium chloride and the.like, which are used .in large "amounts, cannot be effected economic'zally in'practice. VMoreover no economical' use has hitherto been foundforthe larigeamounts of polymerization products simul- 40 taneously formed.. spit of the wo'rk and proposals'made in the ld'concerned, the? said processes haveV threiorenot beenused generally. "I have' now foundthat inthe preparation of v. valuable hydrocarbons from hydrocarbon oils of v fhigher'boiling point, such as mineraloils, tars, ytheir distillation i; cracking, hydrogenation, and f -`destructive hydrogenationV products; as well asr` destructive hydrogenation products ci solid Vcar- `bonaceous materials,'such 'as coals, by thermal 50.sp1itting.'in.the presence Iof metals or `alloys and .of halogens or agents supplying halogens .under the working conditions `which halogens or agents supplyinghalogens may also Abe collectively designated asagents comprisinghaloge'ns, the said drawbacks canbeavoided by leading the'oil to .be treated attemperatures of at least-400 C.' and under such high pressures that the oil. re-

' mains'wholly or partly in the liquidV phase through the reaction vessel at such-a speed .that itis kept at the reaction temperature only for a few 5' minutes, the metals or alloys being. suspended in small amounts in the oil.- Whenworking in' thismanner the pressure is from to 200 atmospheres or more depending on the oil used as initial material. 'I'he temperature in the renc-Q T10 tion vessel is preferably from-about 420 to ,500

C. in contra'stto the temperature of. from 160 to 200 C. employed when working by the processes hitherto known. According tothe present invention,'the oil remains in the reaction chamril ber onlyA for a'.A few minutes, as for'exarnple fromv .1 to rminutes, whereas in the priorprocesses 'this periodamountedio from- 36 to 48 hours. Thus by the process ccording to this inventionv Jextremelyhigh thro puts are and. .this is'of great importance from the point of view of economy. Another importantadvantage of the process according'to this invention'is that only very-small amounts of additions are necesisary in order to obtain a marked eect. The

,amounts 'of added metal and halogenxare generally speaking .les's'than 1 per cent with reference to theinitial oil,`,as `for example between 0.02 and 0.2 per cent ofraluminium and between 0.07 and 0.7.per cent of chlorine. Since the amounts added are so small, -the cost is negligible and the regeneration of the said substances is. unnecessary.. At the same time, the danger of corrosion is entirely avoided or can be prevented A bymuch simpler means and at much Iless cost.` '35- The properties of theY benzine obtained accord'- fing to. this invention when used in automobile or" vlike engines are excellent, the anti-knock rproperties being especially good.V After aV light reiining with sulphuric acidan octane value of from 'I0 to '72 is obtained in a Cooperative Fuel Research'motor.` Still higher octane values can j b eobtained by varying the reaction conditions.

as for example by employing'higher temperatures or allowing the oil to remain in the reaction chamber for longer periods. I v S Furthermore the wasteby gasification 'and formation of tar is very small by reason of the fact that the oil is heated to thehightemperature only for -a very short period of time. .With the 'same initial materials and the same ilnal prodZ ucts, the total waste according to this invention is only from one half to one third of the waste according to the usual non-catalytic crackingj. processes.

"I 'heiprocess according to this invention'may be'carried out in different ways. For example it is possible to work with a straight passage of the .-oil through Vthe reaction chamber, thereby. ob.- taining' mainly benzine, )fuel oil and heating oil.

'Ihe oil which is not converted by the nrst pasesage mayalso be wholly or partly returned to the process, vonly a very small amount of heating oil thus being obtained. The-process may thus be adapted in each' case to the market requirements.

.` The- 'metalsor alloys to. be added may boemployedas such or'in the form. of compounds which are .decomposed to form metals under the' realction conditions. 'Ihe said substances mayjbe mixed with the initial oil orv may be introduced'vv during` operation at a point before or in th'e reaciron, nickel, molybdenum or their alloys. I'heyarapreferably employed in a very nely divided form, as for example in the form of metal pow-- ders asareused for the production of bronze colors. If the metals are to be employed in the form of decomposableeompounds, the metal carbonyls, such as the carbonyls-of iron, nickel or molybdenunior organic 4metal compounds, such as zinc ethyl may 4for-example be employed.

- halogen, as for example hydrogen halides or or- I ganic halogen compounds, such as carbon tetrachloride, ethylene dichloride, chloroform, benzoylchloride is added. The du wan the seid additions is then forced under: a pressure of from 90 to 100 atmospheres by means, of a high-pressure pump through a. preheating coil into 'a' reaction vessel.

The temperature'f the reaction vessel is kept at 460 C. 'I'he oil remains in the reaction vessel for about three; minutes. The product which passes over is cooled and has the following boiling up Ato 200 C. 67.4 per cent up to 275 C., 95.5 per cent;

Its specific gravity at 20 C. is 0.815..

Thefoctane value (anti-knock value) oi' the benzine boilingup to 180 C.i s71.5.

The gasification, calculated with referencev to to the initial oil is 4.5l per cent and the formation or tar, i. e. constituents boiling above 235q C. is 4 percent.

When working under otherwise identical .'conditions but Without the addition ofaluminium and chlorine, the final product has the following boiling range 'up to 180. C. 2.1.0 per cent up to 200 C. 47.0 per cent up to 275 C. 96.3 per cent.

its speelde gravity at 20 c. is osso.v

' .Thus by one passage through the reaction chamber mbre than twice the amount of benzine is obtainedaccording to this invention than acadditions.

It therefore follows that in practice more than mode, benzylchloride, ethylene dbmmlde or, ,twice the yield of bezine'can be obtained with the corresponding iodine compounds or many other organic halogen compounds, eitheralone or in solution or in adm ixture lwith other substancespromoting the' reaction.' Tw or more metals or alloys may also be simultaneously employed; similarly different halogens may be employed at the same time. The metal powders mayJ also be previously activated wth'very smallamounts .of iodine, and in the proce'ssitselfi chlorine maylthen act -as the sec- /The amount of addition to be employed depends f l or; the minar-011 and the desired final produca' 5o the optimum amountcan be ascertained by a preliminary.l experiment in each case'.

' The -following examplejand the accompanying .-1 seli'-exlrvlariatory drawing 'de'scribing the work`- ing up of middle oil obtained ture. of vthis invention, "but mm1 .t

. in uieoufandfhen- 0.20 per cent l carbon' tetra- .any given cracking plant and this is of very great importance from the point of viewof expense. There are also further savings by reason or the smaller gasification, of the lower temperatures, of

the smaller rening waste and of the better exploitation of the' ,resulting benzina -by reason of its better anti-knock properties and better boiling curve.

What I claim isz- A process for treating liquid hydrocarbon mixtur-'esto producen-splitting of 'the hydrocarbons of said.. f mixtures into lower boiling hydrocarbons which comprises adding to said mixtures from ,02 toV 1 percent with reference to said mixtures o1 a; catalyst comprising a' single finely grained vSolidmetal selected from the class consistingyof nickel and molybdenum and from .071:0 .7 percent with reference tp said mixtures of an organic halogen compound, which under the conditions of working is capable of splitting og halogen or halogenvhydrides, .preheating said mixtures in the presence "of the added catalyst. passing Asaid mixtures into a reaction, `maintaining said mixltures `thereinn the absence oi.' addedr` hydrogen fora period of only I to 5 minutes at a temperature of -420- to 550 C. and a.press`ur'e of at least atmospheres, the 'conditions being so correlated 'with the .hydrocarbon mixtures that said mixtures remain for the mostpart 'in the liquid cording to the usual cracking process without, any 

